Process for the preparation of silylated polymers employing a backmixing step
A continuous process for preparing a silylated polymer comprising a silylation step where a prepolymer having reactive functional groups, a first intermediate product, is reacted continuously with a silylating agent in an endcapping tubular reaction unit to form a second intermediate product, and where at least a portion of the second intermediate product is backmixed continuously with the first intermediate product to form the silylated polymer. The continuous process may further comprise a stabilization step, a quenching step or both a stabilization step and a quenching step.
1. A silylated polyurethane having the general formula (10)
X 1 g —(R 1 )[-A 1 C(═O)A 2 R 4 Si(CH 3 ) b (OR 5 ) 3-b ] a-g (10)
wherein
each occurrence of X 1 is a functional group selected from the group consisting of
wherein each occurrence of R 15 is a monovalent hydrocarbon radical containing from about 1 to about 30 carbon atoms and optionally may contain a heteroatom, each occurrence of R 16 is hydrogen, an alkyl group of from 1 to 6 carbon atoms or phenyl, each occurrence of R 17 is hydrogen, an alkyl group of from 1 to about 6 carbon atoms or phenyl and the subscript his an integer of from 1 to about 6;
each occurrence of A 1 is a functional group selected from the group consisting of —O—, —S— and —NH—;
each occurrence of A 2 is a functional group selected from the group consisting of —S—, —NR 6 , where R 6 is selected from the group consisting of hydrogen, an alkyl group containing 1 to about 10 carbon atoms, cycloalkyl group containing from about 5 to about 10 carbon atoms, an aralkyl group containing from about 7 to about 10 carbon atoms, phenyl and —CH[(C═O)OR 7 ]CHR 8 C(═O)OR 7 , where R 7 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms and R 8 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms;
R 1 is an organic group containing from about 50 to about 4,000 carbon atoms and at least one functional group selected from group consisting of —O—, —S—, —OC(═O)NH—, —R 2 NC(═O)NH—, —C(═O)O—, —OC(═O)O—, —OCHR 2 O—, —C(═O)NR 2 — and —NR 2 —, wherein each occurrence of R 2 is independently hydrogen, an alkyl group containing from 1 to about 6 carbon atoms or phenyl;
R 4 is a divalent alkylene group containing from 1 to about 10 carbon atoms, a cycloalkylene group containing from about 5 to about 10 carbon atoms and an arylene group containing from about 6 to about 10 carbon atoms;
each occurrence of R 5 is an alkyl group of from 1 to about 18 carbon atoms or a —R 9 (OR 10 )cOR 11 , wherein R 9 is an alkyl group of from 1 to about 18 carbon atoms, R 10 is a divalent alkylene group of from about 2 to about 4 carbon atoms, and R 11 is an alkyl group of from 1 to about 10 carbon atoms or —C(═O)R 12 , where R 12 is hydrogen, or an alkyl group of from 1 to about 6 carbon atoms, and
the subscripts a, b, c and h are integers wherein a is 1 to about 5, b is 0 to about 2, c is 0 to about 5 and g is 1, with the provisos that (i) a-g is greater than or equal to 1, and (ii) when A 1 is —O— or —S—, then A 2 is —NH—.
2. The silylated polyurethane of claim 1 having a color of less than 50 Pt—Co.
3. The silylated polyurethane of claim 1 having less than about 0.02 weight percent isocyanate.
4. The silylated polyurethane of claim 1 , wherein R 1 is an organic group derived from Formulae (2):
HO—[(R 13 O) d C(═O)NHR 14 NH(C═O)O-] e (R 13 O) f R 13 —OH (2)
wherein each occurrence of R 13 is independently selected from the group consisting of an alkylene group of from about 2 to about 10 carbon atoms, a cycloalkylene group of from about 5 to about 10 carbon atoms, arylene group of from about 6 to about 10 carbon atoms and aralkylene group of from about 7 to about 12 carbon atoms, each occurrence of R 14 is independently selected from the group consisting of an alkylene group of from 1 to about 10 carbon atoms, a cycloalkylene group of from about 5 to about 12 carbon atoms, arylene group of from about 6 to about 10 carbon atoms, aralkylene group of from 7 to 12 carbon atoms, and the subscripts d, e and f are integers and each occurrence of d is from 1 to about 500, e is from 0 to about 5, and f is from 1 to about 500, with the proviso that (d)(e)+f is greater than or equal to about 25.
5. The silylated polyurethane of claim 4 , wherein each R 13 is independently ethylene or propylene and each R 14 is independently hexylene, methylphenylene or
6. The silylated polymer of claim 1 , wherein R 1 is an organic group derived from Formulae (3):
O═C═N—R 14 NHC(═O)O—[(R 13 O) e C(═O)NHR 14 NH(C═O)O-] d (R 13 O) e C(═O)NHR 14 —N═C═O (3)
wherein each occurrence of R 13 is independently selected from the group consisting of an alkylene group of from about 2 to about 10 carbon atoms, a cycloalkylene group of from about 5 to about 10 carbon atoms, arylene group of from about 6 to about 10 carbon atoms and aralkylene group of from about 7 to about 12 carbon atoms, each occurrence of R 14 is independently selected from the group consisting of an alkylene group of from 1 to about 10 carbon atoms, a cycloalkylene group of from about 5 to about 12 carbon atoms, arylene group of from about 6 to about 10 carbon atoms, aralkylene group of from 7 to 12 carbon atoms, and the subscripts c, d and e are integers and each occurrence of c is from about 100 to about 500, d is 1, 2 or 3, and e is from about 100 to about 500.
7. The silylated polyurethane of claim 6 , wherein each R 13 is independently ethylene or propylene and each R 14 is independently hexylene, methylphenylene or
8. The silylated polyurethane of claim 1 , wherein R 1 is an organic group derived from Formulae (4):
O═C═N—R 14 NHC(═O)O—[(R 13 O) d C(═O)NHR 14 NH(C═O)O-] e (R 13 O) f R 13 —OH (4)
wherein each occurrence of R 13 is independently selected from the group consisting of an alkylene group of from about 2 to about 10 carbon atoms, a cycloalkylene group of from about 5 to about 10 carbon atoms, arylene group of from about 6 to about 10 carbon atoms and aralkylene group of from about 7 to about 12 carbon atoms, each occurrence of R 14 is independently selected from the group consisting of an alkylene group of from 1 to about 10 carbon atoms, a cycloalkylene group of from about 5 to about 12 carbon atoms, arylene group of from about 6 to about 10 carbon atoms, aralkylene group of from 7 to 12 carbon atoms, and the subscripts d, e and f are integers and each occurrence of d is from 1 to about 500, e is from 0 to about 5, and f is from 1 to about 500, with the proviso that (d)(e)+f is greater than or equal to about 25.
9. The silylated polyurethane of claim 8 , wherein each R 13 is independently ethylene or propylene and each R 14 is independently hexylene, methylphenylene or
10. A process for the preparation of the silylated polymer comprising
(a) continuously reacting a prepolymer with a silylating agent, by a silylation reaction, to produce a silylated polymer composition;
(b) continuously backmixing at least a first portion of the silylated polymer composition with a loop connected from a downstream outlet to an upstream outlet of a reactor to adjust to at least one upstream process parameter; and
(c) continuously reacting at least a second portion of the silylated polymer composition with a cyclic amide scavenging agent or scavenging package containing at least one cyclic amide scavenging agent to produce the quenched silylated polymer of claim 1 .
11. The process of claim 10 , wherein the cyclic amide scavenging agent is selected from the group consisting of ε-caprolactam and 2-pyrrolidone.
12. The process of claim 10 , wherein the silylating agent of step (a) has the general Formula (5):
YR 4 Si(CH 3 ) b (OR 6 ) 3-b (5)
wherein
Y is a functional group selected from the group consisting of N═C═O, —SH, —OH and —NHR 6 , where R 6 is selected from the group consisting of hydrogen, an alkyl group containing 1 to about 10 carbon atoms, cycloalkyl group containing from about 5 to about 10 carbon atoms, an aralkyl group containing from about 7 to about 10 carbon atoms, phenyl and CH[(C═O)OR 7 ]CHR 8 C(═O)OR 7 , where R 7 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms and R 8 is an alkyl group of from 1 to about 10 carbon atoms, a cycloalkyl group of from about 5 to about 10 carbon atoms, an aryl group of from about 6 to about 10 carbon atoms, and aralkyl group of from about 7 to about 10 carbon atoms;
R 4 is a divalent alkylene group containing from 1 to about 10 carbon atoms, a cycloalkylene group containing from about 5 to about 10 carbon atoms and an arylene group containing from about 6 to about 10 carbon atoms;
each occurrence of R 5 is an alkyl group of from 1 to about 18 carbon atoms or a —R 9 (oR 10 ) c OR 11 , where R 9 is an alkyl group of from 1 to about 18 carbon atoms, R 10 is a divalent alkylene group of from about 2 to about 4 carbon atoms, and R 11 is an alkyl group of from 1 to about 10 carbon atoms or —C(═O)R 12 , where R 12 is hydrogen, or an alkyl group of from 1 to about 6 carbon atoms; and
the subscripts b and c are integers where b is 0 to about 2 and c is 0 to about 5.
13. The process of claim 10 , wherein the prepolymer is at least one prepolymer selected from the group consisting of a chain extended polyol with terminal hydroxyl groups, chain extended polyol with terminal isocyanate groups or a chain extended polyol with both hydroxyl and isocyanate groups.
14. The process of claim 10 further comprising adding a stabilization package to at least one of steps (a), (b) or (c).
15. The process of claim 10 wherein the stabilization package comprises at least one of a hindered phenol or phosphite stabilizer.
16. A silylated polymer composition comprising
(i) at least one silylated polymer of claim 1 ; and
(ii) a stabilization package.
17. The silylated polymer composition of claim 16 , wherein the stabilization package comprises at least one of a hindered phenol or phosphite stabilizer.
18. A system for the continuous production of a silylated polyurethane according to claim 1 comprising
a silylation unit having a tubular reactor with an upstream inlet and a downstream outlet; and
a backmixing loop providing fluid communication from the downstream outlet to the upstream inlet.
19. The system of claim 18 , wherein the backmixing loop comprises at least one of a pump, a heat exchanger, a jacketed static mixer, or a variable diameter endcapping unit.
20. The system of claim 18 , further comprising at least one upstream process chamber comprising a chain extension unit in fluid communication with the inlet, at least one downstream process chamber unit comprising a quenching unit in fluid communication with the outlet, wherein the chain extension unit is connected with an endcapping unit either directly or through a line which connects the two units.